Ketones of the anthraquinone series and process of making same



Patented Sept. 20, 1932 UNITEDSTATES PATENT OFFICE orro BAYERbF rRANxroRT-oN-rnn-Manv, G RMANY, ASSIGNORTO GENERAL LINE WORKS, INC, OF NEW YORK, N. Y., CORPORATION OF DELAWARE xnroivns on THE ANTHRAQUINonn SERIES A'ND rnocnss or MAKING sum No Drawing. Application filed October 9, 1931, Serial 1T0. 567,986, and in Germany October 16,1930.

My present invention relates to ketones of the anthraquinone series and a process of making same. It relates more particularly to ketones of the general formula x r o (wherein one X means hydrogen, the other X a nitroor anamino-group and R means the radical of-aromatic compound containing a labile hydrogen atom);

These ketones are obtained in accordance with this invention by condensing a nitroanthraquinone-2-carboxylic acid halide of the formula chloride and benzene when subjected to Friedel-Craftss reaction yield only resinous products (Ber. d.deutsch. chem. Ges vol. 18 page 2400 and vol. 53,'page.l393) and nitro compounds'are known to be reduced in'the presence of aluminium chloride (Houben- Weyl, Methoden der organischen Chemie; II, editlon, vol. II, page 327), the present process yields in a smooth reaction nitro-anthraquinonyl-arylketones.

. The nitroand amino-ketones thus obtained may be employed as intermediates for the production of dyestuffs. For instance the amino-lretones yield valuable dyestuifs by acylating only or by condensing them with halogenated aromatic compounds.

Instead ofstarting from pure 5- or S-nitroanthraquinone-carboxylic acid halides with the same success the technical mixture of these two nitro compounds may be employed. The products obtained from this mixture 6 understood that my invention is not limited to the particular products nor reacting con ditions mentioned therein.

Example 1 i 200 parts of a mixture of 5- and 8-nitr0- anthraquinone-2-carboxylic acid chloride (melting at 183-185") and 170 parts of diphenyl are dissolved in about 400 parts of dehydrated nitrobenzene. A solution of 105 parts of aluminium chloride in 400 parts of so nitrobenzene is introduced while stirring during 1-2 hours. By weakly cooling-the temperature is maintained at about 30-40". After a further hour the mass is slowly warmed to 40-50. durated about 3 hours the brown solution is introduced while stirring into cold Watercoutaining hydrochloric acid. From this mixture the formed 5-(8-) nitro-Q-anthraquinonyl-diphenyl-ketone is isolated by adding When the reaction has about 1500 parts of petrol and filtering. After washing with water and alcohol the pure ketone is obtained with an excellent yield incol-orless crystals. It melts at 200204 and corresponds to the formula Y o l l V OO (wherein one 1 means hydrogen, the a nitro-group) other .Instead of startmg from the mixture of 5- and S-nitrO-anthraquinone-2-carboxylic; acid chloride one may start with the same success P from the pure ingredients of the saidmixture;

These may be prepared by dissolving the mixture in a 94% sulfuric acid and-.fractionally precipitating. 20 parts of the above mentioned nitroketone are finely divided by dissolvinginsul- V furic acid or by grinding, mixed with 50 parts of crystallized sodiumsulfide and 300 parts of waterand warmed to '8090 for about 1 hour; 9 The precipitate thus formed is filtered and Washed with hot water.ul The mixtureof amino-ketone of the formula r z o I I V V r V e T 1 I (wherein'one Zmeans hydrogen, the other ZiflIl amino-group) which is thus isolated represents a ruby-red powder melting at 200. It shows afiinity to cotton and may be used for the production ofdyestufl's' by condensingittvith acyl-chloridesor halogen-anthraquinones.

By dissolving it in 10 parts (relating to 1 "part of the mixture of amino-ketone) of trichlorobenzene and precipitating, the isomeric components of the mixture may be obtained. The portion filtered at 100 represents dark red needles melting at 2 i2'24c4. It represents about 35% of the starting mixture and is probably 5-amino-2-anthraquinonyl-diphenyl-ketone, In sulfuric acid mixed with formaldehyde it forms a reddish brown solution. f-Its benzoyl compound melts at 244 and dyes cotton from an .olive green vat intense greenish yellow shades.

By cooling the mother liquor or trichlorobenzene and by adding advantageously petrol, the remaining.65% of the starting mixture precipitate. This compound is probably enyl-ketone. It is moreyellowish than the 5-isomeric' compound. Insulfuric acid mixed with formaldehyde it forms a violet brown solution. Itmelts at195-197 9 Its benzoyl compound melts at 257 and dyescotton from 8-amino-2 anthraquinonyl-dipha'reddish violet vat intense greenish yellow shades.

Instead of starting from the isolated mixture of 5- and 8-nitro-anthraquinone-2-carboxylic acid chloride one may start also from the mixture of 5- and S-nitro-anthraquinone- 2-carboxylic acid and effect the formation of the acid chloride and the condensation as a single operation.

E trample 2 I 1 "To a suspension of 50 parts of 5-(8) nitro- ,(whereinone-Z means hydrogen, the other Z an amino-group). It represents a brick-red crystallized powder, soluble in sulfuric. acid with a yellowish, orange shade turning to chestnut-brown after the addition of formaldehyde. v V 7 Example 3 5230 parts of 5-(8) nitro-anthraquinoneQ- carboxylic acid chloride are mixed with 300 parts of 1.3-dimethyl-benzene and 150 parts of carbon disulfide The mixture is allowed to react at 159 with QOpartsof aluminium chloride. After about 12 hours the mass is worked. up asdescribed in the foregoing examples. Themixture of nitro-ketonethus obtained yields on reduction-5-(8) amino-2- anthraquinonyl-2C4'dimethyl-phenyl-ketone of the formula (wherein oneZ means hydrogen, the other Z an amino group) It represents a bright red powder melting at 180-1905.

Ewample 4 By replacing in Example 1 diphenyl by the corresponding amount of diphenyl-ether and condensing it with 5-nitro-anthraquinone-2-carboxylic acid chloride (melting at 198-202 5-nitro-2-anthraquinonyl-J- phenoXy-phenyl-ketone is obtained. It corresponds to the formula Q1) 30 O O O O It melts at 255-260 and may be converted like the aforesaid nitro-ketones into the corresponding amino compounds.

I claim: 1. A process which comprises condensing a nitro-anthraquinone-Q-carboxylic acid halide of the formula C 0-halogen COhaIogen (wherein one Y means hydrogen, the other Y a nitro-group) with diphenyl in the presence of aluminium chloride and reducing the nitroanthraquinone-diphenyl-ketone thus formed.

3. As new compounds the ketones of the anthraquinone series corresponding to the general formula H o 0-R (wherein one X means hydrogen, the other X a nitro or amino group and R means a benzene nucleus which may contain as substituents phenyl, phenoxy, alkyl or halogen) which compounds represent when dry colored powders, having a definite melting point, he-

ing insoluble in water soluble in concentrated sulfuric acid.

4. As new compounds the ketones of the anthraquinone series corresponding to the general formula (wherein one Z means hydrogen, the other Z an amino-group) which compounds represent when dry red powders, having a definite melting point, being insoluble in water, soluble in concentrated sulfuric acid when mixed with formaldehyde with a brownish tint.

5. As a new compound the o-aminoanthraquinone-diphenyl-ketone of the formula O J 00 NH. t

which compound represents when dry dark red needles, melting at 242-244l, being insoluble in water, soluble in concentrated sulfuric acid mixed with formaldehyde with a reddish brown tint, forming a benzoyl compound of melting point 244, which dyes cotton from an olive green vat intense greenish yellow shades.

6. As a new compound the 8-amin0-anthraquinone-diphenyl-ketone of the formula @WOO which compound represents when dry a yellowish red powder, melting at 195497", being insoluble in water, soluble in concentrated sulfuric acid mixed with formaldehyde with a violetish brown tint, forming a benzoyl compound of melting point 257, which dyes cotton from a reddish violet vat intense greenish yellow shades.

In testimony whereof, I afiix my signature.

OTTO BAYER. 

